Interpretation dipolar

The absence of any orientation effect supports this interpretation. Dipolar anisotropic coupling would result from the presence of a hydrogen atom on the carbon carrying the unpaired electron. The nine- and seventeen-lines spectra were previously assigned [68, 71, 72] to the allyl radical... 

Molecular modeling is an indispensable tool in the determination of macromolecular structures from NMR data and in the interpretation of the data. Thus, state-of-the-art molecular dynamics simulations can reproduce relaxation data well [9,96] and supply a model of the motion in atomic detail. Qualitative aspects of correlated backbone motions can be understood from NMR structure ensembles [63]. Additional data, in particular residual dipolar couplings, improve the precision and accuracy of NMR structures qualitatively [12]. 

When both the 1,3-dipoIe and the dipolarophile are unsymmetrical, there are two possible orientations for addition. Both steric and electronic factors play a role in determining the regioselectivity of the addition. The most generally satisfactory interpretation of the regiochemistry of dipolar cycloadditions is based on frontier orbital concepts. As with the Diels-Alder reaction, the most favorable orientation is that which involves complementary interaction between the frontier orbitals of the 1,3-dipole and the dipolarophile. Although most dipolar cycloadditions are of the type in which the LUMO of the dipolarophile interacts with the HOMO of the 1,3-dipole, there are a significant number of systems in which the relationship is reversed. There are also some in which the two possible HOMO-LUMO interactions are of comparable magnitude. 

Calculations at several levels of theory (AMI, 6-31G, and MP2/6-31G ) find lower activation energies for the transition state leading to the observed product. The transition-state calculations presumably reflect the same structural features as the frontier orbital approach. The greatest transition-state stabilization should arise from the most favorable orbital interactions. As discussed earlier for Diels-Alder reactions, the-HSAB theory can also be applied to interpretation of the regiochemistry of 1,3-dipolar cycloaddi-... 

An interpretation based on frontier molecular orbital theory of the regiochemistry of Diels Alder and 1,3-dipolar cycloaddition reactions of the triazepine 3 is available.343 2,4,6-Trimethyl-benzonitrile oxide, for example, yields initially the adduct 6.344... 

From comparison of the optical properties of particles deposited on the same substrate and differing by their organization (Figs. 7 and 8) it can be concluded that the appearance of the resonance peak at 3.8 eV is due to the self-organization of the particles in a hexagonal network. This can be interpreted in terms of mutual dipolar interactions between particles. The local electric field results from dipolar interactions induced by particles at a given distance from each other. Near the nanocrystals, the field consists of the ap-... 

The second reason is related to the misconception that proton dipolar relaxation-rates for the average molecule are far too complicated for practical use in stereochemical problems. This belief has been encouraged, perhaps, by the formidable, density-matrix calculations " commonly used by physicists and physical chemists for a rigorous interpretation of relaxation phenomena in multispin systems. However, proton-relaxation experiments reported by Freeman, Hill, Hall, and their coworkers " have demonstrated that pessimism regarding the interpretation of proton relaxation-rates may be unjustified. Valuable information of considerable importance for the carbohydrate chemist may be derived for the average molecule of interest from a simple treatment of relaxation rates. 

Each of the eight hyperfine resonances is an unresolved quadmpole doublet, due to the quadmpole interaction of Os in the hexagonal Os metal source. The authors have interpreted the hyperfine fields in terms of core polarization, orbital and spin-dipolar contributions. 

Replacement of gas by the nonpolar, e.g., hydrocarbon phase (or oil phase) is used to modify the interactions between molecules in a spread film of investigated long-chain substances [6,15,17,18]. The nonpolar solvent-water interface possesses the advantage over that between gas and water, that the cohesion (i.e., interactions between adsorbed molecules due to dipole and van der Waals forces) is negligible. Thus, at the oil-water interfaces behavior of adsorbates is much closer to ideal, but quantitative interpretation may be uncertain, in particular for the higher chains which are predominantly dissolved in the oil phase to an unknown activity. Adsorption of dipolar substances at the w/a and w/o interfaces changes surface tension and modifies the surface potential of water [15] ... 

These results can be interpreted in terms of competition between recombination of the diradical intermediate and conformational equilibration, which would destroy the stereochemical relationships present in the azo compound. The main synthetic application of azo compound decomposition is in the synthesis of cyclopropanes and other strained-ring systems. Some of the required azo compounds can be made by 1,3-dipolar cycloadditions of diazo compounds (see Section 6.2). 

This is the beauty of this quantity which provides specifically a direct geometrical information (1 /r% ) provided that the dynamical part of Equation (16) can be inferred from appropriate experimental determinations. This cross-relaxation rate, first discovered by Overhau-ser in 1953 about proton-electron dipolar interactions,8 led to the so-called NOE in the case of nucleus-nucleus dipolar interactions, and has found tremendous applications in NMR.2 As a matter of fact, this review is purposely limited to the determination of proton-carbon-13 cross-relaxation rates in small or medium-size molecules and to their interpretation. 

Attempts to interpret the corresponding build-up curves according to the Lipari-Szabo approach lead to inconsistent results (for instance, order parameters greater than unity). This indicates that these remote correlations are probably not of infra-molecular origin but would rather arise from znfer-molecular dipolar interactions which could become significant when some contacts exist between neighbouring aliphatic chains. This... 

The AO composition of the SOMO can often be deduced from the dipolar hyperfine matrix, particularly when the radical has enough symmetry to restrict possible hybridization. Thus an axial hyperfine matrix can usually be interpreted in terms of coupling to a SOMO composed of a single p- or d-orbital. A departure from axial symmetry may be due to spin orbit coupling effects, if (for example) /) Az and Ax AyxP(gx gy). If the departure from axial symmetry is larger, it is usually caused by d-orbital hybridization. The procedure is best illustrated by examples. 

Fohlisch99 reported a remarkable dependence of the electron spectra of quino-cyclopropenes on their structure. As shown in Table 9, the merocyanine-like quino-cyclopropenes show positive solvatochromy when they contain an anthraquinonoid chromophore (198), but negative solvatochromy when they contain a benzoquino-noid system (199). This can be interpreted in terms of a markedly increased participation of dipolar resonance forms in the ground state of the benzoquinonoid 199 compared to the anthraquinonoid 198. From the dipole moment of 198 (9.4 D99 ) the dipolar contribution was estimated to be in the range of 23%. 

Computer simulation of the experimental spectra in the frozen solution points to a spin-localized structure independent of the temperature. This interpretation is unambiguous because, in the solid state, the dipolar contributions of the hyperfine interaction A(dip) for all three principal... 

The spin dynamics of solids whose primary or sole nuclear interactions (ignoring the omnipresent Zeeman and isotropic chemical shift terms) are dipolar interactions among a very large number of nuclei present interpretive and theoretical challenges... 

Similarly, in a 1,3-dipolar cycloaddition of DMAD to the conformationally locked cyclic a-alkoxycarbonylnitrone (727), bicyclic ring systems, containing a nitrogen atom at the bridgehead position have been synthesized. A mechanistic interpretation of the origin of the fused pyrroles (729) includes the intermediate formation of the aziridine ring in (728) (Scheme 2.303) (820). 

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